US5242979A - Organosilicon compositions containing hydrocarbon elastomers - Google Patents

Organosilicon compositions containing hydrocarbon elastomers Download PDF

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US5242979A
US5242979A US07/593,161 US59316190A US5242979A US 5242979 A US5242979 A US 5242979A US 59316190 A US59316190 A US 59316190A US 5242979 A US5242979 A US 5242979A
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carbon
composition
elastomer
double bonds
prepolymer
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Paquita E. Barnum
Richard L. Brady
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National Starch and Chemical Investment Holding Corp
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Hercules LLC
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Assigned to HERCULES INCORPORATED, A CORP OF DE reassignment HERCULES INCORPORATED, A CORP OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BARNUM, PAQUITA E., BRADY, RICHARD L.
Priority to DE69122024T priority patent/DE69122024T2/de
Priority to ES91116964T priority patent/ES2093056T3/es
Priority to AU85624/91A priority patent/AU647184B2/en
Priority to EP91116964A priority patent/EP0482404B1/en
Priority to CA002052799A priority patent/CA2052799C/en
Priority to MX9101445A priority patent/MX9101445A/es
Priority to JP25821291A priority patent/JP3180826B2/ja
Priority to KR1019910017485A priority patent/KR100192725B1/ko
Priority to BR919104315A priority patent/BR9104315A/pt
Priority to TW080107968A priority patent/TW258746B/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • This invention is directed to cross-linked organosilicon polymers and cross-linkable organosilicon prepolymers comprised of polycyclic hydrocarbon residues and cyclic polysiloxane or siloxysilane residues linked through carbon to silicon bonds, further comprising hydrocarbon elastomer.
  • Brittleness can result in cracking or poor adhesive strength (e.g., poor adhesion of copper foil to circuit board laminate).
  • this invention is directed to a polymeric composition
  • a polymeric composition comprising (a) a continuous phase of a cross-linked organosilicon polymer comprised of alternating (i) polycyclic hydrocarbon residues derived from polycyclic polyenes having at least two non-aromatic, non-conjugated carbon-carbon double bonds in their rings and (ii) residues derived from the group consisting of cyclic polysiloxanes and tetrahedral siloxysilanes, linked through carbon to silicon bonds, and (b) a discontinuous phase of a low molecular weight hydrocarbon elastomer having at least two hydrosilation reactable carbon-carbon double bonds.
  • this invention is directed to a prepolymer composition
  • a prepolymer composition comprising (a) a hydrosilation cross-linkable organosilicon prepolymer which is the partial reaction product of (i) polycyclic polyenes having at least two non-aromatic, non-conjugated hydrosilation reactive carbon-carbon double bonds in their rings and (ii) cyclic polysiloxanes or tetrahedral siloxsilanes having at least two hydrosilation reactive .tbd.SiH groups wherein at least one of (i) or (ii) has at least three reactive groups, and (b) hydrocarbon elastomer having at least two hydrosilation reactable carbon-carbon double bonds.
  • FIG. 1 depicts an end view of a test sample used in the double torsion test.
  • FIG. 2 depicts a side view of the sample. The end to the left of the figure is the precrack end.
  • FIG. 3 is a depiction of the testing of the sample in double torsion.
  • FIG. 1 an end view of the test sample used in the double torsion test is depicted.
  • T describes the thickness of the test sample
  • W describes the width of the test sample.
  • 03 T defines a thickness of 30% of T and "0.4 T” defines a thickness of 40% of T.
  • FIG. 2 a side view of the sample is depicted where, as in FIG. 1., "T” as in is the thickness of the sample, “0.3 T” defines a thickness of 30% of T and “0.4 T” defines a thickness of 40% of T. "L” is the length of the sample and "3/4" describes the length of the sample which is beveled to a maximum depth of 35% of the total thickness of he sample.
  • FIG. 3 the testing of the sample is depicted in double torsion.
  • T is the total thickness of the sample
  • W is the total width of the sample.
  • Load is the load applied to the sample during the test.
  • Tc is the reduced thickness of the sample, and
  • M is the length of a moment arm used in the test.
  • SiH is be used to describe hydrosilation reactable .tbd.SiH groups.
  • Cyclic polysiloxanes useful in forming the products of this invention have the general formula: ##STR1## wherein R is hydrogen, a saturated, substituted or unsubstituted alkyl or alkoxy radical, a substituted or unsubstituted aromatic or aryloxy radical, n is an integer from 3 to about 20, and R is hydrogen on at least two of the silicon atoms in the molecule.
  • reactants of Formula (I) include, e.g., tetra- and penta-methylcyclotetrasiloxanes; tetra-, penta-, hexa- and hepta-methylcyclopentasiloxanes; tetra-, penta- and hexa-methylcyclohexasiloxanes, tetraethyl cyclotetrasiloxanes and tetraphenyl cyclotetrasiloxanes.
  • the tetrahedral siloxysilanes are represented by the general structural formula: ##STR2## wherein R is as defined above and is hydrogen on at least two of the silicon atoms in the molecule.
  • reactants of Formula (II) include, e.g., tetrakisdimethylsiloxysilane, tetrakisdiphenylsiloxysilane, and tetrakisdiethylsiloxysilane.
  • the tetrakisdimethylsiloxysilane is the best known and preferred species in this group.
  • the polymers and prepolymers of this invention may also contain other hydrosilation reactable polysiloxanes bearing two or more SiH groups.
  • they may contain linear, short chain SiH terminated polysiloxanes having the general formula: ##STR3## wherein n is 0 to 1000 and R is alkyl or aryl, preferably methyl or phenyl, as described by Leibfried in U.S. patent application Nos. 07/419,429 and 07/419,430, (now U.S. Pat. Nos. 5,013,809 and 5,077,134, respectively) supra.
  • These linear, short chain SiH terminated polysiloxanes impart flexibility to the cured polymers and can be used to produce elastomers.
  • Polycyclic polyenes useful in preparing the composition of this invention are polycyclic hydrocarbon compounds having at least two non-aromatic, carbon-carbon double bonds.
  • Illustrative are compounds selected from the group consisting of cyclopentadiene oligomers (e.g., dicyclopentadiene (“DCPD”), tricyclopentadiene (also known as “cyclopentadiene trimer”) and tetracyclopentadiene), norbornadiene dimer, bicycloheptadiene (i.e., norbornadiene) and its Diels-Alder oligomers with cyclopentadiene (e.g., dimethanohexahydronaphthalene), and substituted derivatives of any of these, e.g., methyl dicyclopentadienes.
  • cyclopentadiene oligomers such as dicyclopentadiene and tricylopentadiene. Two or more polycyclic polyenes can
  • the hydrocarbon component comprises (a) at least one low molecular weight (typically having a molecular weight less than 1,000, preferably less than 500) polyene having at least two non-aromatic carbon-carbon double bonds highly reactive in hydrosilation (they may contain other less reactive (including unreactive) double-bonds, provided that those double bonds do not interfere with the reactivity of the highly reactive double bonds; but, compounds having only two highly reactive double bonds are preferred), the carbon-carbon double bonds being either in an alpha, beta or gamma position on a linear carbon moiety, next to two bridgehead positions in a strained polycyclic aliphatic ring structure, or in a cyclobutene ring, and (b) at least one polycyclic polyene having at least two chemically distinguishable non-aromatic, non-conjugated
  • component (a) examples include 5-vinyl-2-norbornene, o-, m- or p-diisopropenylbenzene, o-, m- or p-divinylbenzene, diallyl ether, diallyl benzene, dimethanohexahydronaphthalene and the symmetrical isomer of tricyclopentadiene.
  • component (b) by “having at least two chemically distinguishable carbon-carbon double bonds” it is meant that at least two carbon-carbon double bonds have widely different rates of reaction in hydrosilation and that one of the double bonds will react prior to substantial reaction of the other double bond(s). This first double bond must be quite reactive in hydrosilation.
  • Reactive double bonds include those that are next to two bridgehead positions in a strained polycyclic aliphatic ring structure or in a cyclobutene ring, as per component (a) of the embodiment described directly above.
  • the other carbon-carbon double bond(s) may be any other non-aromatic, 1,2-disubstituted non-conjugated carbon-carbon double bond that is not next to two bridgehead positions in a strained polycyclic aliphatic ring structure and is not in a cyclobutene ring.
  • Exemplary are dicyclopentadiene and the asymmetrical isomer of tricyclopentadiene.
  • Preferred, for electronic applications are polymers made from dicyclopentadiene, tricyclopentadiene and methylhydrocyclosiloxane.
  • the reactions for forming the organosilicon prepolymers and polymers of this invention are described in U.S. patent application Nos. 07/419,429, 07/419,430 and 07/422,214, (now U.S. Pat. Nos. 5,013,809, 5,077,134 and 5,008,360, respectively) and U.S. Pat. No. 4,900,779 and 4,902,731, supra.
  • the reactions for forming the prepolymer and for forming a polymer from the prepolymer can be promoted thermally or by the addition of a hydrosilation catalyst or radical generators such as peroxides and azo compounds.
  • Hydrosilation catalysts include metal salts and complexes of Group VIII elements.
  • the preferred hydrosilation catalysts contain platinum (e.g., PtCl 2 , dibenzonitrile platinum dichloride, platinum on carbon, etc.).
  • the preferred catalyst in terms of both reactivity and cost, is chloroplatinic acid (H 2 PtCl 6 .6H 2 O).
  • PC072 and PC075 are preferred for curing prepolymers.
  • Catalyst concentrations of 0.0005 to about 0.05% by weight of platinum, based on the weight of the monomers, are preferred.
  • the correct relative ratios of reactants and the platinum catalyst are simply mixed and brought to a temperature at which the reaction is initiated and proper temperature conditions are thereafter maintained to drive the reaction to substantial completion (typically, with a ratio of carbon-carbon double bonds to SiH groups of about 1:1, when 70 to 90% of the SiH groups are consumed).
  • thermoset polymers result when the ratio of carbon-carbon double bonds of (b) to SiH groups in (a) is in the range of from about 0.5:1 up to about 1.3:1, more preferably from about 0.8:1 up to about 1.1:1.
  • the alternating residues form a cross-linked thermoset structure.
  • the prepolymers can be prepared as disclosed in U.S. patent application No. 07/422,214, (now U.S. Pat. No. 5,008,360) and U.S. Pat. Nos. 4,900,779 and 4,902,731, supra.
  • the initial product of the reaction at lower temperatures e.g., about 25° to about 80° C.
  • the prepolymers generally have 30 to 70% of the SiH groups reacted, and when liquids are desired preferably about 30 to 60% of the SiH groups reacted.
  • Such prepolymers can be recovered and subsequently transferred to a mold for curing.
  • prepolymers are prepared using polycyclic polyenes having at least two chemically distinguishable non-aromatic, non-conjugated carbon-carbon double bonds in their rings.
  • Illustrative are compounds selected from the group consisting of dicyclopentadiene, asymmetrical tricyclopentadiene, and methyl dicyclopentadiene, and substituted derivatives of any of these. Preferred is dicyclopentadiene.
  • Such prepolymers can also be prepared with the hydrocarbon combinations described in U.S. patent application No. 07/422,214, (now U.S. Pat. No. 5,008,360) supra.
  • the prepolymers including the viscous, flowable liquid prepolymers, are stable at room temperature for varying periods of time, and cure upon reheating to an appropriate temperature, e.g., about 100° to about 250° C. Often, additional catalyst is added to the prepolymer prior to cure to further promote the reaction.
  • a second type of prepolymer can be prepared by a process described in U.S. Pat. No. 4,900,779 and U.S. patent application Nos. 07/419,429 and 07/419,430 (now U.S. Pat. Nos. 5,013,809 and 5,077,134 respectively).
  • an olefin rich prepolymer is prepared by reacting a large excess of polycyclic polymers with cyclic siloxanes or tetrahedral siloxysilanes.
  • the olefin rich organosilicon prepolymer is blended with additional cyclic polysiloxane or tetrahedral siloxysilane before cure.
  • organosilicon prepolymers are made with a large excess of carbon-carbon double bonds available for reaction with SiH groups. That is, the ratio of carbon-carbon double bonds in the rings of the polycyclic polyenes used to form the polycyclic polyene residues (a) to SiH groups in the cyclic polysiloxanes and tetrahedral siloxysilanes used to form the cyclic polysiloxane or tetrahedral siloxysilanes residues (b) is greater than 1.8:1, preferably greater than 1.8:1 and up to 2.2.:1.
  • the prepolymers of this embodiment are generally in the form of flowable liquids, which are stable at room temperature.
  • the most stable prepolymers are formed at a double bond to SiH ratio of about 2:1 since virtually all polyene is reacted and excess polycyclic polyene need not be removed. (Due to their odor, the presence of unreacted polycyclic polyenes is undesirable. When necessary or desirable, unreacted polycyclic polyenes can be stripped, e.g., using a rotoevaporator, to form odorless compositions.)
  • cross-linked polymers are formed by mixing the prepolymers with the polysiloxanes/siloxysilanes such that the total ratio of non-aromatic, non-conjugated carbon-carbon double bonds in the rings of the polycyclic polyenes used to form the polycyclic polyene residues (a) to SiH groups in the polysiloxanes and siloxysilanes used to form the polysiloxane/siloxysilane residues (b) is in the ratio of 0.4:1 to 1.7:1; preferably 0.8:1 to 1.3:1, most preferably about 1:1, and curing the mixture in the presence of a hydrosilation catalyst.
  • the organosilicon prepolymers are reacted with the polysiloxanes and/or siloxysilanes to form a cross-linked polymer in a mold.
  • the prepolymers and polysiloxanes/siloxysilanes are stored separately and are blended before entering the mold.
  • the hydrosilation catalyst may be present in either or both stream(s) or injected directly into the mixer. The reaction is exothermic and proceeds rapidly so that the polymer gels and the product can be removed from the mold in minutes. The components of the blends are completely stable until they are mixed. This permits indefinite ambient storage of the materials.
  • the blend components can be premixed and stirred in a tank. These blends have low viscosity and are pumpable. Addition of catalyst and/or application of heat can be used to cure the prepolymer composition. The reaction may be carried out in an extruder, mold or oven, or the blend may be applied directly on a substrate or part.
  • reaction speed and its accompanying viscosity increase can be controlled by use of a cure rate retardant (complexing agent), such as N,N,N',N'-tetramethylethylenediamine, diethylenetriamine or phosphorus compounds.
  • a cure rate retardant such as N,N,N',N'-tetramethylethylenediamine, diethylenetriamine or phosphorus compounds.
  • additives such as fillers and pigments are readily incorporated.
  • Carbon black, vermiculite, mica, wollastonite, calcium carbonate, silica, fused silica, fumed silica, glass spheres, glass beads, ground glass and waste glass are examples of fillers which can be incorporated.
  • Fillers can serve either as reinforcement or as fillers and extenders to reduce the cost of the molded product. Glass spheres are useful for preparing low density composites. When used, fillers can be present in amounts up to about 85%.
  • Fiber reinforced composites may be made with the prepolymers of this invention. They can contain as much as 80%, preferably 30 to 60%, by weight, of fibrous reinforcement. Fibrous reinforcement useful in this invention includes glass, etc., as described in U.S. Pat. Nos. 4,900,779 and 4,902,731.
  • the polymers of this invention have excellent electrical insulating properties and resistance to moisture. Often, they have high glass transition temperatures.
  • the polymers and prepolymers of this invention are well-suited for electronic applications, e.g., composites, adhesives, encapsulants, potting compounds and coatings. They are especially useful for preparing laminates, such as those used for printed circuit boards.
  • Stabilizers are useful to maintain storage stability of B stage materials and thermal oxidative stability of the final product.
  • Preferred are bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-(3,5-di-tert-butyl-4-hydroxybenzyl)butylpropanedioate, (available as TinuvinTM 144 from Ciba-Geigy Corp., Hawthorne, NY) or a combination of octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (also known as octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate) (available as Naugard® 76 from Uniroyal Chemical Co., Middlebury, CT) and bis(1,2,2,6,6-pentamethyl-4-piperidinylsebacate) (available as Tinuvin 765® from Ciba-Gei
  • elastomers of this invention improves the peel strength of the cured polymer when it is adhered to copper, and the toughness of the cured polymer, without significantly affecting other properties. That is, there is not a significant effect on the dielectric constant, glass transition temperature or thermal coefficient of expansion. These properties make the resins useful in the preparation of composites, coating, adhesives, circuit board laminates, molded circuit boards, encapsulants and potting resins.
  • an elastomer In order for an elastomer to be effective in toughening the glassy polymer without significantly affecting other properties, there are several requirements. First, there is a reaction between the prepolymer and elastomer in order for there to be adhesion between phases of the polymer. Second, the polymer and elastomer should form two phases.
  • the elastomer should have two or more hydrosilation reactable carbon-carbon double bonds. Elastomers having large numbers of double bonds tend to react with the prepolymer to form a one phase system.
  • the hydrocarbon rubber may be hydrogenated to reduce the number of carbon-carbon double bonds, so that phase separation does occur.
  • the elastomer should have no more than 50 mole % >C ⁇ C ⁇ , preferably no more than 25 mole % >C ⁇ C ⁇ and most preferably no more than 15 mole % >C ⁇ C ⁇ .
  • the elastomer is preferably present as micron-sized particles forming a secondary phase.
  • the particles are in the range of 0.001 to 50 micron in diameter, preferably 0.01 to 10 micron in diameter, and most preferably 0.1 to 5 micron in diameter.
  • the preferred hydrocarbon elastomers have a molecular weight of less than 100,000.
  • Elastomer is generally used in an amount of 0.5 to 20%, preferably 3 to 12%, and most preferably 5 to 10%, by weight.
  • Elastomer may be added to the prepolymer or during prepolymer synthesis.
  • a 1500 ppm chloroplatinic acid/dicyclopentadiene (CPA/DCPD) catalyst was prepared by sparging with nitrogen for five minutes in a glass container 0.15 parts CPA, and then adding 100 parts DCPD and stirring at 50° to 70° C. for 1 hour. Afterwards the complex was allowed to cool to room temperature.
  • This catalyst will be referred to as catalyst A.
  • Catalyst B was a commercially available catalyst, PC072, from Huls America, Bristol, PA.
  • a 200 ppm chloroplatinic acid/dicyclopentadiene catalyst was prepared in the same manner as used to prepared catalyst A using 0.02 parts CPA and 100 parts DCPD.
  • Catalyst D was a commercially available catalyst, PC075, from Huls America, Bristol, PA.
  • a 3000 ppm chloroplatinic acid/dicyclopentadiene catalyst was prepared in the same manner as catalyst A using 0.30 parts CPA and 100 parts DCPD.
  • This example demonstrates preparation of prepolymer without rubber.
  • catalyst A (CPA/DCPD complex) were added. Stirring was carried out at ambient temperature to 30° C. until 99% of the more reactive double bonds (half of the double bonds of the polycyclic polyenes) were hydrosilylated.
  • the gel time of the resultant prepolymer solution was measured by placing 2 to 3 drops of the solution directly onto a Fischer-Johns melting point apparatus at 156° C. and stirring with a wooden applicator stick until it gelled. It was found to be greater than 12 minutes. At this time, 0.06 parts catalyst B were added. The gel time was found to be 2 minutes.
  • the prepolymer solution was transferred to a second glass container, and the container was placed under aspirator vacuum followed by high vacuum to remove 99% of the toluene solvent.
  • the gel time of the resulting prepolymer was tested again. It was found to be 1.75 minutes at 157° C.
  • the prepolymer was then poured into a 80° C. Teflon lined stainless steel mold, and placed into a 80° C. oven for cure with a nitrogen purge.
  • the cure cycle was heating from 80° C. to 168° C. over a one hour period, holding between 168° C. to 175° C. for one hour, heating from 175° C. to 255° C. over 1 hour, holding at 255° C. for 4 hours, and cooling slowly in the oven to room temperature over 12 hours.
  • Samples were cut from the cured plaque with a diamond saw and tested for: (1) Tg and thermal expansion coefficient by thermal mechanical analyzer (TMA), (2) flex modulus and strength according to ASTM D790, (3) phase morphology by transmission electron microscopy (TEM), and (4) G 1c fracture toughness by ASTM E 399-83 (1983) (modified as described in S. A. Thompson et al, SAMPE Journal Vol. 24, No. 1, pp. 47-49 (1988)) in Examples 1 to 8 and 20 and by a double torsion test (See, for example, A. J. Kinloch and R. J. Young, Fracture Behavior of Polymers, Applied Science Publishers, New York, 1983.) in Examples 9-19.
  • the double torsion tests were carried out as follows: First, the plaques were cut into 1.5 inch by 4.5 inch by 0.125 inch samples. On both sides of the rectangles, a 45 degree groove was cut down the center lengthwise with a 45 degree diamond wheel. The groove was beveled at a depth of 30% of the samples thickness, except than it was beveled to a maximum depth of 35% of the total thickness starting 0.75 inches from one end of the rectangle. The resulting sample is illustrated in FIG. 1.
  • the groove was such that one end had a reduced thickness section.
  • the sample was then precracked at the end bevelled to a depth of 35% of the thickness, by tapping a razor blade into the end.
  • the beveled groove prevents the precrack from propagating the length of the sample before testing.
  • the sample was then tested in double torsion as illustrated in FIG. 3.
  • Example 1 All dimensions were measured by a digital micrometer. The results for Example 1 are shown in Table 1.
  • This example demonstrates preparation of prepolymer with rubber.
  • Tinuvin® 144 as an antioxidant, 21.6 parts toluene, 12 parts of a 30% (W/W) solution of Trilene® 65 low molecular weight EPDM rubber (Uniroyal Chemical Company, Middlebury, CT) in toluene, 57.3 parts of a 28.9% w/w mixture of cyclopentadiene trimer in DCPD, 55.11 parts MHCS, and 2.84 parts catalyst A (CPA/DCPD complex).
  • the glass container was sealed (it had a pressure release device) and the container was placed in a 40° C. water bath. Stirring was carried out in a 40° C. water bath for six hours and then at ambient temperature until 99% of the more reactive double bonds (half of the double bonds of the polycyclic polyenes) were reacted.
  • the gel time of the resultant prepolymer solution was measured by placing 2 to 3 drops of the solution directly onto a Fischer-Johns melting point apparatus at 155° C. and stirring with a wooden applicator stick until it gelled. It was found to be greater than 11 minutes. At this time, 0.012 parts catalyst B were added. The gel time was found to be 2 minutes, 15 seconds.
  • the prepolymer solution was transferred to a second glass container, and the container was placed under aspirator vacuum followed by high vacuum to remove 99% of the toluene solvent.
  • the gel time of the resulting prepolymer was tested again. It was found to be 2.5 minutes at 159° C.
  • the prepolymer was then poured into a 60° C. Teflon lined stainless steel mold, and placed into a 60° C. oven for cure with a nitrogen purge.
  • the cure cycle was heating from 60° C. to 160° C. over a two hour period, holding between 160° and 170° C. for one hour, heating from 170° to 235° over 2 hours, holding at 235° C. for 4 hours, and cooling slowly in the oven to room temperature over 12 hours.
  • Example 2 The results for Example 2 are shown in Table 1. Addition of 3% low molecular weight EPDM rubber (Trilene 65) had no significant effect on the glass transition and of the polymer, but it caused a doubling of the fracture toughness value (as compared to Example 1).
  • Tinuvin® 144 as an antioxidant, 2 parts toluene, 52.9 parts of a 29% w/w mixture of cyclopentadiene trimer in DCPD, 40 parts of a 30% w/w solution of TrileneTM 65 low molecular weight EPDM rubber in toluene, 51.1 parts MHSC, and 2.85 parts catalyst A (CPA/DCPD complex).
  • the glass container was sealed and a nitrogen bleed attached.
  • the container was placed in a 44° C. bath and stirring was carried out for six hours, followed by stirring at ambient temperature until 99% of the more reactive double bonds (half of the double bonds of the polycyclic polyenes) were reacted.
  • the gel time of the resultant prepolymer solution was measured by placing 2 to 3 drops of the solution directly onto a Fischer-Johns melting point apparatus at 157° C. and stirring with a wooden applicator stick until it gelled. It was found to be greater than 11 minutes. At this time, 0.013 parts catalyst B were added. The gel time was found to be 2.5 minutes at 158° C.
  • the prepolymer solution was transferred to a second glass container, and the container was placed under aspirator vacuum followed by high vacuum to remove 99% of the toluene solvent.
  • the gel time of the resulting prepolymer was tested again. It was found to be .75 minutes at 157° C.
  • the prepolymer was then poured into a 60° C. Teflon lined stainless steel mold, and placed into a 60° C. oven for cure with a nitrogen purge.
  • the cure cycle was heating from 60° C. to 160° C. over a two hour period, holding between 160° and 170° C. for one hour, heat from 170° to 235° over 2 hours, holding at 235° C. for 4 hours, and cooling slowly in the oven to room temperature over 12 hours.
  • This example shows preparation of a glass reinforced laminate containing no rubber.
  • a resin solution was prepared in a glass container by adding together 98.9 parts MHCS, 107.2 parts of a 28.8% solution of cyclopentadiene trimer in DCPD, 2.17 parts TinuvinTM 144, 55 parts hexane, and 11 parts catalyst A.
  • the container was placed in a large 25° C. water bath and the solution was stirred until all of the more reactive double bonds were reacted.
  • the gel time of the resultant prepolymer solution was found to be 1 minute 20 seconds at 171° C.
  • the prepolymer solution was poured into a stainless steel container equipped with two bars above the container, as described in example 4.
  • the glass fabric was pulled through the solution and bars, and hung to cure in an oven at 150° C. for approximately 150-175 seconds, after which it was removed and allowed to cool.
  • the resultant prepreg was substantially tack free and contained about 45 weight percent prepolymer.
  • Two four layer copper topped laminates were prepared by stacking prepregs (prepared as described above) between Teflon sheets and aluminum caul plates, with a piece of copper on the top prepreg, and placing the stack in a room temperature press at 27.8 pounds per square inch. The press was heated to 165° C., held for 1 hour, and then cooled. The laminates were then post cured at 200° C. in a nitrogen sparged oven for 2 hours.
  • the copper peel strength of the laminate was measured using an Instron equipped with a bottom grip that allowed the copper to be pulled at 90.0 degrees from the laminate at all times.
  • the units of data obtained from the Instron are pounds per linear inch.
  • the results are shown in Table 1.
  • the peel strength for this resin containing no rubber was 3.15 pounds per linear inch ("pli").
  • a prepolymer was prepared using 49 parts MHCS, 36.7 parts DCPD, 17 parts cyclopentadiene trimer, 1.65 parts NaugardTM 76 as antioxidant, 0.34 parts TinuvinTM 765 as antioxidant, 43.25 parts of a 23.5% (W/W) solution of low molecular weight EPDM rubber (TrileneTM65) in toluene, and 5.4 parts catalyst A.
  • the gel point of the prepolymer was 1 minute, 45 seconds at 170° C. Copper topped glass laminates of the resin were prepared as described in Example 4.
  • Example 5 The results for Example 5 are shown in Table 1.
  • the copper peel strength for Example 5 was 5.1 pli compared to 3.15 pli for Example 4, containing no EPDM rubber.
  • This example demonstrates preparation of a prepolymer without rubber, using 5-vinyl-2-norbornene.
  • the resin was poured into a Teflon-lined stainless steel mold, that had been treated with a release agent, and placed into a 100° C. oven for cure with a nitrogen purge according to the following schedule: heating at 100° C. for one hour, 165° C. for one hour and 220° C. for four hours, and cooling slowly in the oven over 12 hours. Samples were cut from the cured plaque and tested as described in Example 1. The results are shown in Table 1. The fracture toughness value for this resin was similar to the fracture toughness value obtained for the sample containing trimer of Example 1.
  • This example demonstrates preparation of prepolymer with a combination of 5-vinyl-2-norbornene and trimer, without rubber.
  • Solvent was evaporated from the prepolymer solution as described in Example 1, and the prepolymer was poured into a 100° C. Teflon-lined stainless steel mold. The filled mold was placed in a 100° C. oven for cure with a nitrogen purge. The cure cycle was heating from 100° C. to 159° C. over 0.5 hour, holding between 159°-161° C. for one hour, heating to 250° C. over one hour, and holding at 250°-260° C. for 4.5 hours, and cooling slowly in the oven over 12 hours. Samples were cut from the cured plaque and tested as described in Example 1. The results are shown in Table 1. The fracture toughness value for this sample was similar to the fracture toughness value obtained for the sample of Example 1.
  • This example demonstrates preparation of prepolymer with a combination of 5-vinyl-2-norbornene and trimer, with rubber.
  • Example 7 The fracture toughness value for this sample increased 5.5 fold relative to Example 7, but the glass transition temperature for the polymer containing rubber dropped relative to the control containing no rubber.
  • This example describes preparing a prepolymer without rubber.
  • a prepolymer solution comprising 150.6 parts MHCS, 168.2 parts of a mixture of cyclopentadiene dimer and trimer (30% trimer in final polymer), 23.3 parts catalyst C, 15.8 parts NaugardTM76/TrinuvinTM765/toluene at a 50/10.1/60.1 ratio, and 79.6 parts toluene was made by the method in Example 1.
  • the prepolymer solution was further activated with 80 ppm Pt (from a 9.05% wt solution of Catalyst B in toluene) to attain a gel time of 2 minutes 1 second at 160° C. (Gel times were measures using 4 drops of resin solution on a Fischer-Johns melting point apparatus.)
  • the prepolymer solution was placed in a rotary evaporator for 2.5 to 3 hours at 40° C. to strip greater than 99% of the toluene off.
  • the prepolymer was then poured into a 100° C. preheated stainless steel mold and placed in a programmable oven for cure with a nitrogen purge.
  • the cure cycle was heating from room temperature to 160° C. at 2° C./minute, holding at 160° C. for 1 hour, heating from 160° C. to 250° C. at 1° C./minute, holding at 250° C. for 4 hours, and cooling slowly in the oven to room temperature over 12 hours.
  • the resulting plaque was transparent.
  • This example demonstrates the procedure for adding rubber to prepolymer, and the effectiveness of low molecular weight EPDM.
  • the prepolymer solution as described in Example 9 was activated with 75 ppm Pt as Catalyst B to give a gel time of 1 min 55, seconds at 160° C.
  • prepolymer prepolymer still in solution
  • TrileneTM 65 low moleculer weight EPDM rubber To 95 parts of prepolymer (prepolymer still in solution) was added 5 parts TrileneTM 65 low moleculer weight EPDM rubber. The solution was stirred for 15 hours at room temperature. The EPDM rubber dissolved to form a slightly cloudy solution.
  • the prepolymer solution blend was then rotovaped, cured, and tested as in Example 9.
  • the prepolymer blend after stripping was slightly cloudy (small scale phase separation as confirmed by optical microscopy) at room temperature.
  • the cured plaque was opague (two phases).
  • Example 9 To the prepolymer solution of Example 9 was added 75 ppm Pt as Catalyst B to give a gel time of 1 min, 55 sec at 160° C. To 95 parts of activated prepolymer in solution was added 5 parts TrileneTM 67 according to the procedure in Example 10. All other procedures were as in Example 9. The stripped prepolymer blend and the cured plaque were phase separated.
  • Example 9 To the prepolymer of Example 9 was added 80 ppm Pt as Catalyst B to give a gel time of 1 min, 55 sec at 160° C. To 95 parts activated prepolymer in solution was added 5 parts low molecular weight polyisoprene according to the procedure of Example 10. All other procedures were as in Example 9. The stripped prepolymer blend and resulting plaque were clear, indicating no phase separation had occurred.
  • This example demonstrates the effectiveness of partially hydrogenated low molecular weight polyisoprene.
  • the purpose of using hydrogenated material is to reduce the number of carbon/carbon double bonds and limit reaction with the prepolymer on cure. This limited reaction promotes phase separation, which provides toughness without significantly affecting Tg or TCE.
  • Example 9 To the prepolymer solution of Example 9 was added 75 ppm Pt as Catalyst B to give a gel time of 1 min, 59 sec at 160° C. To 95 parts of the activated prepolymer in solution was added 5 parts LIR290 90% hydrogenated low molecular weight polyisoprene (Nissho Iwai American Corp., New York, N.Y.) according to the procedure of Example 10. All other procedures were according to Example 9. Both solvent stripped prepolymer blend and cured plaque were phase separated.
  • This example demonstrates the ineffectiveness at toughening the resin of low molecular weight ethylene-propylene copolymer (no diene).
  • Example 9 To the prepolymer solution of Example 9 was added 78 ppm Pt as Catalyst B to give a gel time of 1 minute 52 seconds at 160° C. To 95 parts of the activated prepolymer in solution was added 5 parts Trilene CP80 low molecular weight ethylene-propylene copolymer (Uniroyal Chemical, Middlebury, Conn.) according to the procedure in Example 10. All other procedures were as in Example 9. The solvent-stripped prepolymer blend and cured plaque were phase separated.
  • Trilene CP80 low molecular weight ethylene-propylene copolymer Uniroyal Chemical, Middlebury, Conn.
  • a prepolymer solution was produced as follows. To a glass container was added 111.1 parts DCPD, 2.1 parts DCPD/CPA catalyst concentrate (0.275 weight % Pt in DCPD) and 55.9 parts toluene. This mixture was heated to 50° C. for 1 hour and then cooled to room temperature to form mixture B. Mixture A was prepared by combining 110.8 parts MHCS, 4.26 parts NaugardTM 76 and 0.85 parts TinuvinTM 765 in a glass container. Mixture A was heated to 70° C., and mixture B was added dropwise with stirring to maintain a reaction temperature less than 100° C. The reaction solution was heated at 70° C. after addition was complete. The reaction considered completed when 99% of the norbornene carbon-carbon double bonds of the DCPD were reacted (as shown by NMR).
  • the prepolymer solution was activated with 10 ppm Pt as Catalyst B to give a gel time of 2 minutes 1 second at 160° C.
  • the prepolymer was stripped, cured, and tested according to the procedures of Example 9. The stripped prepolymer and cured plaque were both clear.
  • Example 15 The prepolymer solution of Example 15 was activated with 10 ppm Pt as Catalyst B. To 95 parts of activated prepolymer in solution was added 5 parts TrileneTM 65 low molecular weight EPDM rubber according to the procedure of Example 10. All other procedures were according to Example 9. The stripped prepolymer blend and cured plaque were phase separated.
  • This example shows the improved solubility and effectiveness in toughening of very low molecular weight EPDM.
  • This example shows the effectiveness of low molecular weight butyl rubber.
  • Example 17 To the prepolymer solution of Example 17 was added 10 ppm Pt as Catalyst B. 4.2 parts of KaleneTM 800 low molecular weight butyl rubber was dissolved in 20.1 parts toluene. This rubber solution was then mixed into the prepolymer solution at a prepolymer/rubber ratio of 95/5. The predissolving of the rubber was necessary because of its higher viscosity relative to the other rubbers. All other procedures were as in Examples 9 and 10. The stripped prepolymer blend and cured plaque were both phase separated.
  • This example shows the effectiveness of partially hydrogenated low molecular weight styrene-butadiene rubber ("SBR”) in toughening the resin.
  • SBR partially hydrogenated low molecular weight styrene-butadiene rubber
  • This example shows the effectiveness of partially hydrogenated low molecular weight butadiene rubber.
  • RiconTM 131 low molecular weight butadiene rubber (Colorado Chemical Specialties, Inc., Grand Junction, Colo.) was hydrogenated and filtered as in Example 19. The rubber solution was then dried fully in a vacuum oven at 60° C. for greater than 2 hours. NMR results showed 92% hydrogenation of the double bonds.
  • Example 17 To the prepolymer solution of Example 17 was added 10 ppm Pt as Catalyst B. To 95 parts of the activated prepolymer in solution was added 5 parts hydrogenated Ricon 131 according to the procedure of Example 10. All other procedures were as in Example 9. The cured plaque was phase separated.

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US07/593,161 US5242979A (en) 1990-10-05 1990-10-05 Organosilicon compositions containing hydrocarbon elastomers
MX9101445A MX9101445A (es) 1990-10-05 1991-10-04 Composiciones de organosilicio que contienen elastomeros hidrocarburo
ES91116964T ES2093056T3 (es) 1990-10-05 1991-10-04 Composiciones de organosilicio que contienen elastomeros hidrocarburos.
AU85624/91A AU647184B2 (en) 1990-10-05 1991-10-04 Organosilicon compositions containing hydrocarbon elastomers
EP91116964A EP0482404B1 (en) 1990-10-05 1991-10-04 Organosilicon compositions containing hydrocarbon elastomers
CA002052799A CA2052799C (en) 1990-10-05 1991-10-04 Organosilicon compositions containing hydrocarbon elastomers
DE69122024T DE69122024T2 (de) 1990-10-05 1991-10-04 Kohlenwasserstoff-Elastomere enthaltende Organosiliconmassen
KR1019910017485A KR100192725B1 (ko) 1990-10-05 1991-10-05 탄화수소 탄성중합체를 함유하는 유기실리콘 조성물
JP25821291A JP3180826B2 (ja) 1990-10-05 1991-10-05 炭化水素エラストマーを含む有機シリコン組成物
BR919104315A BR9104315A (pt) 1990-10-05 1991-10-07 Composicao compreendendo um polimero de organossilicio reticulado e composicao de pre-polimero
TW080107968A TW258746B (cs) 1990-10-05 1991-10-09

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US5298588A (en) * 1992-02-05 1994-03-29 Hercules Incorporated Organosilicon polymers, and dyes, exhibiting nonlinear optical response
US5373077A (en) * 1993-04-19 1994-12-13 Hercules Incorporated Fully substituted cyclopolysiloxanes and their use for making organosilicon polymers
US5451637A (en) * 1994-05-10 1995-09-19 Hercules Incorporated Organosilicon compositions prepared from unsaturated elastomeric polymers
US5512376A (en) * 1994-06-20 1996-04-30 Hercules Incorporated Nonpolar polymers comprising antiplasticizers
US5852092A (en) * 1997-02-11 1998-12-22 Johnson Matthey, Inc. Organosilicon-containing compositions having enhanced adhesive properties
US5859105A (en) * 1997-02-11 1999-01-12 Johnson Matthey, Inc. Organosilicon-containing compositions capable of rapid curing at low temperature
US6524716B2 (en) 2000-07-27 2003-02-25 The Goodyear Tire & Rubber Company Method for the preparation of a diene polymer interpenetrated with a polysiloxane
US20030232361A1 (en) * 1993-10-26 2003-12-18 Affymetrix, Inc. Nucleic acid array preparation using purified phosphoramidites
US6773809B1 (en) * 1999-11-08 2004-08-10 Kaneka Corporation Copper foil with insulating adhesive
US6800439B1 (en) 2000-01-06 2004-10-05 Affymetrix, Inc. Methods for improved array preparation
US6806361B1 (en) 2000-03-17 2004-10-19 Affymetrix, Inc. Methods of enhancing functional performance of nucleic acid arrays
US6822066B2 (en) 2002-11-18 2004-11-23 Dow Corning Corporation Organosiloxane resin-polyene materials
US6833450B1 (en) 2000-03-17 2004-12-21 Affymetrix, Inc. Phosphite ester oxidation in nucleic acid array preparation
US20050119473A1 (en) * 2000-03-17 2005-06-02 Affymetrix, Inc. Phosphite ester oxidation in nucleic acid array preparation
US7005259B1 (en) 2000-06-01 2006-02-28 Affymetrix, Inc. Methods for array preparation using substrate rotation
US7157564B1 (en) 2000-04-06 2007-01-02 Affymetrix, Inc. Tag nucleic acids and probe arrays
US20070037951A1 (en) * 2004-07-29 2007-02-15 Musa Osama M Siloxane resins with oxetane functionality
US20070255054A1 (en) * 2005-12-30 2007-11-01 Affymetrix, Inc. Oligonucleotide synthesis with intermittent and post synthetic oxidation
US20080071023A1 (en) * 2006-09-12 2008-03-20 Shin-Etsu Chemical Co., Ltd. Silicone-based curable composition containing polycyclic hydrocarbon group
US20100298171A1 (en) * 2009-05-22 2010-11-25 Affymetrix, Inc. Apparatus for polymer synthesis
US9447454B2 (en) 2003-10-23 2016-09-20 The Rockefeller University Method of purifying RNA binding protein-RNA complexes
CN114940824A (zh) * 2022-05-25 2022-08-26 歌尔股份有限公司 发声装置的振膜及其制备方法、发声装置

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US5298536A (en) * 1992-02-21 1994-03-29 Hercules Incorporated Flame retardant organosilicon polymer composition, process for making same, and article produced therefrom
US5523374A (en) * 1992-12-03 1996-06-04 Hercules Incorporated Curable and cured organosilicon compositions
US5391678A (en) * 1992-12-03 1995-02-21 Hercules Incorporated Curable and cured organosilicon compositions
JP4921657B2 (ja) * 2001-09-05 2012-04-25 株式会社カネカ 光学材料用硬化性組成物、光学用材料、その製造方法およびそれを用いた発光ダイオード
JP2003073551A (ja) * 2001-09-06 2003-03-12 Kanegafuchi Chem Ind Co Ltd 硬化性組成物、硬化物及びその製造方法
JP5676068B2 (ja) * 2001-09-06 2015-02-25 株式会社カネカ 硬化性組成物、硬化物、その製造方法およびその硬化物により封止された発光ダイオード
US6841647B2 (en) 2001-11-06 2005-01-11 National Starch And Chemical Investment Holding Corporation Fluid resistant silicone encapsulant
JP4520251B2 (ja) * 2003-10-10 2010-08-04 信越化学工業株式会社 硬化性組成物
JP4504077B2 (ja) * 2004-04-23 2010-07-14 株式会社カネカ 硬化性組成物の製造方法
WO2007109282A2 (en) * 2006-03-21 2007-09-27 Dow Corning Corporation Silicone-organic elastomer gels
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US5298588A (en) * 1992-02-05 1994-03-29 Hercules Incorporated Organosilicon polymers, and dyes, exhibiting nonlinear optical response
US5373077A (en) * 1993-04-19 1994-12-13 Hercules Incorporated Fully substituted cyclopolysiloxanes and their use for making organosilicon polymers
US20030232361A1 (en) * 1993-10-26 2003-12-18 Affymetrix, Inc. Nucleic acid array preparation using purified phosphoramidites
US5451637A (en) * 1994-05-10 1995-09-19 Hercules Incorporated Organosilicon compositions prepared from unsaturated elastomeric polymers
GB2289283A (en) * 1994-05-10 1995-11-15 Hercules Inc Organosilicon polymers prepared from unsaturated elastomeric polymers
GB2289283B (en) * 1994-05-10 1998-03-25 Hercules Inc Organosilicon compositions prepared from unsaturated elastomeric polymers
US5512376A (en) * 1994-06-20 1996-04-30 Hercules Incorporated Nonpolar polymers comprising antiplasticizers
US5852092A (en) * 1997-02-11 1998-12-22 Johnson Matthey, Inc. Organosilicon-containing compositions having enhanced adhesive properties
US5859105A (en) * 1997-02-11 1999-01-12 Johnson Matthey, Inc. Organosilicon-containing compositions capable of rapid curing at low temperature
US6773809B1 (en) * 1999-11-08 2004-08-10 Kaneka Corporation Copper foil with insulating adhesive
US6800439B1 (en) 2000-01-06 2004-10-05 Affymetrix, Inc. Methods for improved array preparation
US6806361B1 (en) 2000-03-17 2004-10-19 Affymetrix, Inc. Methods of enhancing functional performance of nucleic acid arrays
US6833450B1 (en) 2000-03-17 2004-12-21 Affymetrix, Inc. Phosphite ester oxidation in nucleic acid array preparation
US20050119473A1 (en) * 2000-03-17 2005-06-02 Affymetrix, Inc. Phosphite ester oxidation in nucleic acid array preparation
US7157564B1 (en) 2000-04-06 2007-01-02 Affymetrix, Inc. Tag nucleic acids and probe arrays
US7005259B1 (en) 2000-06-01 2006-02-28 Affymetrix, Inc. Methods for array preparation using substrate rotation
US20060147981A1 (en) * 2000-06-01 2006-07-06 Affymetrix, Inc. Methods for array preparation using substrate rotation
US6524716B2 (en) 2000-07-27 2003-02-25 The Goodyear Tire & Rubber Company Method for the preparation of a diene polymer interpenetrated with a polysiloxane
US6822066B2 (en) 2002-11-18 2004-11-23 Dow Corning Corporation Organosiloxane resin-polyene materials
US9447454B2 (en) 2003-10-23 2016-09-20 The Rockefeller University Method of purifying RNA binding protein-RNA complexes
US20070037951A1 (en) * 2004-07-29 2007-02-15 Musa Osama M Siloxane resins with oxetane functionality
US7414103B2 (en) 2004-07-29 2008-08-19 National Starch And Chemical Investment Holding Corporation Siloxane resins with oxetane functionality
US20070255054A1 (en) * 2005-12-30 2007-11-01 Affymetrix, Inc. Oligonucleotide synthesis with intermittent and post synthetic oxidation
US20080071023A1 (en) * 2006-09-12 2008-03-20 Shin-Etsu Chemical Co., Ltd. Silicone-based curable composition containing polycyclic hydrocarbon group
US20100298171A1 (en) * 2009-05-22 2010-11-25 Affymetrix, Inc. Apparatus for polymer synthesis
CN114940824A (zh) * 2022-05-25 2022-08-26 歌尔股份有限公司 发声装置的振膜及其制备方法、发声装置
CN114940824B (zh) * 2022-05-25 2024-03-08 歌尔股份有限公司 发声装置的振膜及其制备方法、发声装置

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BR9104315A (pt) 1992-06-09
AU647184B2 (en) 1994-03-17
EP0482404A2 (en) 1992-04-29
JPH0693181A (ja) 1994-04-05
DE69122024D1 (de) 1996-10-17
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AU8562491A (en) 1992-04-09
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EP0482404A3 (en) 1993-02-17
KR100192725B1 (ko) 1999-06-15
CA2052799C (en) 2002-03-05
ES2093056T3 (es) 1996-12-16

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